CN105914374A - Nitrogen-doped carbon-coated molybdenum selenide/graphene core-shell array sandwich structure composite material, preparation method and application thereof - Google Patents
Nitrogen-doped carbon-coated molybdenum selenide/graphene core-shell array sandwich structure composite material, preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a nitrogen-doped carbon-coated molybdenum selenide/graphene core-shell array sandwich structure composite material, a preparation method and application thereof. The method includes: dissolving selenium powder in hydrazine hydrate to form a solution A; dissolving a sodium molybdate dehydrate solution in water to form a solution B; mixing the solutions to form a reaction solution, placing a vertical grapheme collector electrode material growing on a carbon cloth in the reaction solution to carry out hydrothermal reaction, and then conducting washing and drying to obtain a VG-MoSe2 core-shell array structure; dissolving dopamine hydrochloride in water, then soaking the VG-MoSe2 core-shell array structure in the dopamine hydrochloride aqueous solution, carrying out water bath polymerization, and performing washing drying; and carbonizing the dopamine polymerized core-shell array structure under high temperature condition in protective atmosphere, thus obtaining the nitrogen-doped carbon-coated molybdenum selenide/graphene core-shell array sandwich structure composite material. When used as a sodium ion negative electrode material, the constructed composite material has high reversible charge-discharge capacity, long cycle life and excellent rate performance.
Description
Technical field
The present invention relates to anode material of lithium-ion battery technical field, be specifically related to a kind of nitrogen-doped carbon cladding
Composite of selenizing molybdenum/Graphene nucleocapsid array sandwich structure and preparation method thereof and as sodium ion electricity
The application of pond negative material.
Background technology
Energy crisis and environmental problem are two challenging greatly of facing of current mankind society, and exploitation cleaning is renewable
Novel energy become the urgent needs of society.In the middle of current various new energy source technology, lithium
Ion secondary battery, due to high-energy-density, high working voltage, advantages of environment protection, captures rapidly
Portable electronic market, and become the primary selection of electric automobile and large-scale energy storage system.But due to lithium
Resource reserve is limited and skewness, and result in it cannot effectively meet power lithium-ion rechargeable battery
Huge needs, and raised further and the price of lithium associated materials, increase the cost of its battery, from
And hinder the development of novel energy industry.Therefore the relevant energy storage of honest alternative lithium ion battery is developed
It is crucial that technology becomes urgent problem.
Sodium aboundresources, development cost is low, and sodium has similar embedding and deviates from the features such as mechanism to lithium,
Make sodium ion secondary battery become the first-selection of alternative lithium rechargeable battery, and become society
Study hotspot.But due to sodium ion radiusCompare lithium ionGreatly, sodium ion
Migrating in electrode material slowly, deintercalation process is complicated, causes reversible capacity and high rate performance poor.Cause
This explore have the sodium-ion battery material of high reversible capacity and good circulation stability to a new generation's sodium from
The development of sub-secondary cell has great importance.The MoSe of layer structure2, owing to having bigger layer
The embedding of spacing (0.67nm), beneficially sodium ion and abjection, and it is big to embed offer for sodium ion
Space, it is to avoid volumetric expansion during embedding sodium, thus maintain stablizing of structure, there is higher storage simultaneously
Sodium capacity (400-800mA hg-1), therefore MoSe2Research as sodium ion negative material becomes
Current study hotspot.But two-dimensional structure MoSe2Material due to the van der Waals interaction of layer Yu interlayer,
Easily reuniting during charge discharge, cause electrolyte and active substance effectively contacts reduction,
Electrode reversible capacity rapid decay.It addition, pure MoSe2Electronic conductivity is the highest so that it is as sodium
During ion secondary battery negative pole, high rate performance is relatively low, it is difficult to bear the discharge and recharge of larger current density.Therefore,
Improve two-dimensional layer MoSe2Structural stability and improve electronic conductivity be MoSe2Material is as sodium
The key scientific problems that the application of ion secondary battery negative material is urgently to be resolved hurrily.
At present, by by layer structure MoSe2It is combined with reduced graphene, suppresses it to reunite, increase it
Electric conductivity, improves sodium ion diffusion rate.It addition, to MoSe2Carry out surface modification or cladding, press down
Make the dissolving of many selenides that its charge and discharge process produces, thus improve its storage sodium stability and times
Rate performance.Layer structure selenides modifying surface, carbon is coated with, and the thickness of its carbon thin layer, microcosmic are tied
Structure, doping situation, affect its interlayer distance, electric conductivity and electron transfer rate thereof, thus affect
Its storage sodium performance.Although above method can improve MoSe to a certain extent2As sodium ion negative pole
Chemical property, but its chemical property such as reversible capacity and high rate performance is from industrial applications also
There is a segment distance, improvement of still needing.
Summary of the invention
Object of the present invention is to provide a kind of nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array folder
Composite of core structure and its preparation method and application, the composite of this structure is used as sodium ion negative pole
During material, with high reversible charge/discharge capacity, long circulation life and excellent high rate performance.
A kind of nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure sodium ion negative material and
Its preparation method, described MoSe2Nanometer sheet intersecting vertical is grown in vertical graphene array, and all
The carbon-coating of even one layer of N doping of cladding, defines sandwich structure, and the carbon thickness of the N doping of described cladding is
5-10nm。
The present invention passes through with vertical Graphene (VG) as skeleton, MoSe2Nanometer sheet intersecting vertical grows
In vertical graphene array, the carbon (NC) of N doping is that clad builds nucleocapsid array sandwich structure
VG@MoSe2@NC composite, thus obtain high reversible capacity and excellent high rate performance.
A kind of preparation of the composite of nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure
Method, comprises the following steps:
(1) selenium powder is dissolved in hydrazine hydrate, forms solution A；
(2) Sodium Molybdate Dihydrate is dissolved in water, forms solution B；
(3) solution A is mixed homogeneously with solution B, form reactant liquor, the vertical of carbon cloth will be grown in
Graphene collector material is placed in this reactant liquor, carries out hydro-thermal reaction, the most scrubbed, dry,
To VG-MoSe2Nucleocapsid array structure；
(4) take dopamine hydrochloride to be dissolved in water, form dopamine hydrochloride aqueous solution, then by step
(3) VG-MoSe of gained2Nucleocapsid array structure is immersed in dopamine hydrochloride aqueous solution, and water-bath gathers
Close, scrubbed dry, obtain the nucleocapsid array structure of dopamine polymerization；
(5) the nucleocapsid array structure being polymerized by step (4) gained dopamine, calcines under protective atmosphere
Carbonization, obtains the composite of nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure, i.e.
VG@MoSe2@NC。
Following as the preferred technical solution of the present invention:
In step (1), in described solution A, the concentration of selenium is 0.2-0.6mmolmL-1(i.e. mmol/mL).
In step (2), in described solution B, the concentration of sodium molybdate is 0.02-0.1mmolmL-1。
In step (3), in described solution A, selenium is 1.5～2.5 with the mol ratio of sodium molybdate in solution B:
1, further preferably, for 2:1.Further preferably, hydro-thermal reaction 12-24 is carried out at 160-200 DEG C little
Time.
In step (4), in described dopamine hydrochloride aqueous solution, the concentration of dopamine is 3-7mg mL-1,
Being polymerized 12-24 hour 70 DEG C of-90 DEG C of water-baths, further preferably, water-bath temperature is 80 DEG C.
In step (5), described protective atmosphere is nitrogen or argon, in nitrogen or argon shield
Under, calcining heat is 500-800 DEG C, and calcination time is 2-6 hour.
The composite of described nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure,
MoSe2Content is 0.2-0.5mg cm-2。
The composite of nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure is particularly as sodium
Ion battery cathode material, the VG@MoSe that will obtain2The direct little section of@NC composite is as sodium
Ion battery negative pole assembled battery.The preparation of negative pole is by step (5) gained VG@MoSe2@NC
Composite is cut into slices, and barrier film uses Whatman glass fibre, and electrolyte is with 1molL-1NaClO4
For solute, volume ratio be the ethylene carbonate (EC) of 1:1 be solvent with dimethyl carbonate (DMC),
And adding the fluorinated ethylene carbonate of 5.0wt.%, negative pole uses sodium sheet, the assembling process of battery
All at full argon and water oxygen content, the glove box less than 0.1ppm completes.
The lithium ion battery assembled carries out constant current charge-discharge test, discharge and recharge electricity after placing 24 hours
Pressure is 3.0V～0.01V, and in 25 ± 1 DEG C of environment, the capacity of lithium ion battery negative, charge and discharge are measured in circulation
Electricity cycle performance and multiplying power property.
Compared with prior art, present invention have the advantage that
(1) present invention uses hydro-thermal, the method that water-bath combines, the flexible nitrogen-doped carbon bag of preparation with calcining
Cover selenizing molybdenum/Graphene nucleocapsid array sandwich structure sodium ion negative material, with low cost, preparation technology letter
Single, it is easy to accomplish large production.
(2) the VG@MoSe prepared by2@NC is flexible nucleocapsid array sandwich structure, nitrogen-doped carbon bag
Coating is 5-10nm thickness, many selenides when being conducive to improving the electric conductivity of material and effective discharge and recharge
Dissolve.
(3) the VG@MoSe prepared by2@NC is prepared as sodium ion negative pole, then be direct shearing, saves
Go the preparation of slurry, coating, the loaded down with trivial details electrode preparation process such as drying.
(4) the VG@MoSe prepared by2@NC composite, vertical Graphene skeleton provides good
Electron propagation ducts, the carbon coating layer of N doping improves the electric conductivity of electrode and inhibits charge and discharge process
The dissolving thus overcome the fast inferior position of decay of the many selenides of middle generation, it is achieved that have high cyclical stability,
High rate capability, the sodium-ion battery negative pole of high charge-discharge capacity.
(5) the method is simple to operate, yield is big, and clad is uniform.The sandwich nucleocapsid battle array that the present invention prepares
Array structure VG@MoSe2@NC sodium ion negative material has flexible support, high specific discharge capacity, length
The advantages such as cyclical stability and excellent high rate performance, have broad application prospects in novel energy field.
Accompanying drawing explanation
Fig. 1 is the nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure prepared by embodiment 1
The process schematic of composite, wherein, in Fig. 1, (a) is the vertical Graphene being grown in carbon cloth
(VG), in Fig. 1, (b) is VG-MoSe2Nucleocapsid array structure, in Fig. 1, (c) is VG@MoSe2@NC。
Fig. 2 is the nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure of preparation in embodiment 1
The XRD spectra of composite.
Fig. 3 is the nucleocapsid array structure VG@MoSe of preparation in embodiment 12Different multiples SEM figure,
Wherein, in Fig. 3, (a) is the nucleocapsid array structure VG@MoSe of preparation in embodiment 12Low range
SEM schemes, the nucleocapsid array structure VG@MoSe of preparation during (b) is embodiment 1 in Fig. 32High power
Rate SEM is schemed.
Fig. 4 is to prepare nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure in embodiment 1
The different multiples SEM figure of composite and photo in kind thereof, wherein, in Fig. 4, (a) is embodiment 1
The low range of the middle composite preparing nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure
SEM schemes, and in Fig. 4, (b) prepares nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid battle array in being embodiment 1
The high magnification SEM figure of the composite of row sandwich structure, in Fig. 4, (c) prepares nitrogen in being embodiment 1
The photo in kind of the composite of doping carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure.
Fig. 5 is to prepare nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure in embodiment 1
Circulating battery stability prepared by composite.
Fig. 6 is to prepare nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure in embodiment 1
Battery high rate performance prepared by composite.
Detailed description of the invention
Below by embodiment the present invention made and further illustrating, but the invention is not limited in
Following example.
Embodiment 1
(1) the selenium powder dispersing and dissolving of 4mmol is taken in the middle of the hydrazine hydrate of 10mL, room temperature 25 DEG C
Under the conditions of, stirring 30min, define the solution A of claret, in solution A, the concentration of selenium is
0.4mmolmL-1；
(2) take 2mmol Sodium Molybdate Dihydrate to be dissolved in 60mL deionized water, form solution B, molten
In liquid B, sodium molybdate concentration is 0.33mmolmL-1；
(3) take the solution A of 10mL and the solution B of 60mL, mixing and stirring, transfer to anti-
Answering in the middle of still, vertical Graphene (VG) collector material that then 5 × 5cm is grown in carbon cloth is placed in
Wherein, 200 DEG C of hydro-thermal reactions 24 hours, washing, it is dried, obtains VG-MoSe2Nucleocapsid array structure；
(4) weigh the dopamine hydrochloride of 0.2g, be dissolved in 30mL deionized water formation solution, so
After by VG-MoSe2Nucleocapsid array structure soaks wherein, 80 DEG C of polyreactions of water-bath 24 hours, washing
It is dried, obtains the nucleocapsid array composite material that dopamine was polymerized；
(5) nucleocapsid array composite material dopamine being polymerized under argon atmosphere, 600 DEG C
High temperature cabonization 4 hours, obtains the compound of nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure
Material, i.e. VG@MoSe2@NC；
(6) by VG@MoSe2@NC composite is directly cut to small pieces, as sodium-ion battery electricity
Pole.By assembling button sodium ion half-cell, with VG@MoSe2@NC composite be half-cell just
Pole, with whatman glass fibre for half-cell barrier film, with 1mol L-1NaClO4For solute, volume
It is solvent than ethylene carbonate (EC) and the dimethyl carbonate (DMC) for 1:1, and adds 5.0wt.%
Fluorinated ethylene carbonate be electrolyte, with sodium sheet for button half-cell negative pole, the assembling process of battery is complete
All at full argon and water oxygen content, the glove box less than 0.1ppm completes.
In conjunction with hydro-thermal, the method that water-bath combines with calcining prepares nitrogen-doped carbon cladding selenizing molybdenum/Graphene core
As shown schematically in fig. 1, wherein, in Fig. 1, (a) is growth to the preparation process of shell array sandwich structure
At the vertical Graphene (VG) of carbon cloth, in Fig. 1, (b) is VG-MoSe2Nucleocapsid array structure, figure
In 1, (c) is VG@MoSe2@NC。
Nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure sodium ion negative material passes through X
Ray diffraction spectra test (XRD), as in figure 2 it is shown, prepare VG@MoSe for the present embodiment 12@NC
The XRD figure spectrum of composite.According to Fig. 2, the VG@MoSe of the present embodiment 1 preparation2@NC
Composite has the diffraction maximum of VG, with MoSe2Diffraction maximum (JCPDS Card No.29-0914).
As shown in Fig. 3 (a-b), the carbon-coating VG-MoSe of uncoated N doping2SEM picture, maintain
The structure of vertical graphene array, and growing the vertical of one layer of cross-bridging on graphene film
MoSe2Nanometer sheet, nanoscale twins thickness is 20-30 nanometer.Defined with carbonization by dopamine polymerization
After carbon coating layer, as shown in Fig. 4 (a-b), it can be seen that vertical-growth MoSe on Graphene2
Nanometer sheet is thickening, and lamellar structure is difficult to distinguish, defines the MoSe of carbon cladding2.As illustrated in fig. 4 c,
VG@MoSe2@NC has good flexibility.According to calculating of poor quality before and after reaction, nitrogen can be calculated
Doping carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure sodium ion negative material (i.e. nitrogen-doped carbon bag
Cover the composite of selenizing molybdenum/Graphene nucleocapsid array sandwich structure) in MoSe2Content be about 0.27
mg cm-2。
The lithium ion battery assembled carries out constant current charge-discharge test, discharge and recharge electricity after placing 24 hours
Be 3.0V～0.01V between nip, in 25 ± 1 DEG C of environment circulation measure sodium-ion battery negative pole capacity,
Charge-discharge performance and multiplying power property.
After being assembled into lithium ion battery, carry out various electrochemical property test.As seen from Figure 5, sodium from
Sub-battery is at 200mA g-1There is under electric current density 785.6mAh g-1Discharge capacity first, through 400
After secondary circulation, its discharge capacity still has 534.8mAh g-1, coulombic efficiency maintains more than 99%, aobvious
Show capability retention and the cyclical stability of excellence.Fig. 6 show negative pole material prepared by the present embodiment
The high rate performance figure of material, this material shows the most excellent high rate performance, 0.2,0.5,1.0 and 2.0A
g-1Under electric current density, capacity respectively reaches 538,470,395 and 300mAh g-1.When electric current is from 2.0A g-1
Return to 0.2A g-1Time, and after circulating 100 times, battery capacity returns to 535mAh g-1。
Embodiment 2
(1) the selenium powder dispersing and dissolving of 3mmol is taken in the middle of the hydrazine hydrate of 10mL, room temperature 25 DEG C
Under the conditions of, stirring 30min, define the solution A of claret, in solution A, the concentration of selenium is
0.3mmolmL-1；
(2) take 1.5mmol Sodium Molybdate Dihydrate to be dissolved in 50mL deionized water, form solution B,
In solution B, sodium molybdate concentration is 0.03mmolmL-1；
(3) take the solution A of 10mL and the solution B of 50mL, mixing and stirring, transfer to anti-
Answering in the middle of still, vertical Graphene (VG) collector material that then 3 × 3cm is grown in carbon cloth is placed in
Wherein, 200 DEG C of hydro-thermal reactions 16 hours, washing, it is dried, obtains VG-MoSe2Nucleocapsid array structure；
(4) weigh the dopamine hydrochloride of 0.15g, be dissolved in 30mL deionized water formation solution,
Then by VG-MoSe2Nucleocapsid array structure soaks wherein, 80 DEG C of water-bath polyreactions 18 hours, washes
Wash dry, obtain the nucleocapsid array composite material that dopamine was polymerized；
(5) the nucleocapsid array composite material being polymerized by dopamine is under nitrogen protection atmosphere at 700 DEG C
Calcine 3 hours, obtain nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array composites sandwich structures,
I.e. VG@MoSe2@NC；
(6) by VG@MoSe2@NC composite is directly cut to small pieces, as electrode.By group
Dress button sodium ion half-cell, with VG@MoSe2@NC composite is half-cell positive pole, with
Whatman glass fibre is half-cell barrier film, with 1molL-1NaClO4For solute, volume ratio is 1:1
Ethylene carbonate (EC) and dimethyl carbonate (DMC) be solvent, and add 5.0wt.% fluoro
Ethylene carbonate is electrolyte, and with sodium sheet for button half-cell negative pole, the assembling process of battery is all being filled
Full argon and water oxygen content complete less than in the glove box of 0.1ppm.
According to calculating of poor quality before and after reaction, nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid battle array can be calculated
MoSe in row sandwich structure sodium ion negative material2Content be about 0.25mg cm-2。
Nitrogen-doped carbon prepared by the present embodiment is coated with selenizing molybdenum/Graphene nucleocapsid array sandwich structure sodium
After ion negative material is assembled into sodium ion secondary battery, carry out various electrochemical property test.Sodium ion
Battery is at 200mA g-1There is under electric current density 789.3mAh g-1Discharge capacity first, through 400
After secondary circulation, its discharge capacity still has 536.8mAh g-1, coulombic efficiency maintains more than 99%, aobvious
Show capability retention and the cyclical stability of excellence.From the multiplying power of negative material prepared by the present embodiment
In performance map, this material shows the most excellent high rate performance, 0.2, and 0.5,1.0 and 2.0A g-1Electricity
Under current density, capacity respectively reaches 539,471,394 and 302mAh g-1.When electric current is from 2.0A g-1Return
To 0.2A g-1Time, and after circulating 100 times, battery capacity returns to 534mAh g-1。
Embodiment 3
(1) the selenium powder dispersing and dissolving of 6mmol is taken in the middle of the hydrazine hydrate of 10mL, under normal temperature condition,
Stirring 30min, defines the solution A of claret, and in solution A, the concentration of selenium is 0.6mmolmL-1；
(2) Sodium Molybdate Dihydrate taking 3mmol is dissolved in 60mL deionized water, forms solution B,
In solution B, sodium molybdate concentration is 0.05mmolmL-1；
(3) take the solution A of 10mL and the solution B of 60mL, mixing and stirring, transfer to anti-
Answering in the middle of still, vertical Graphene (VG) collector material that then 6 × 6cm is grown in carbon cloth is placed in
Wherein, 200 DEG C of hydro-thermal reactions 12 hours, washing, it is dried, obtains VG-MoSe2Nucleocapsid array structure；
(4) weigh the dopamine hydrochloride of 0.3g, be dissolved in 30mL deionized water formation solution, so
After by VG-MoSe2Nucleocapsid array structure soaks wherein, 80 DEG C of water-bath polyreactions 12 hours, washing
It is dried, obtains the nucleocapsid array composite material that dopamine was polymerized；
(5) the nucleocapsid array composite material being polymerized by dopamine is under argon atmosphere at 800 DEG C
Calcine 2 hours, obtain nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array composites sandwich structures,
I.e. VG@MoSe2@NC；
(6) by VG@MoSe2@NC composite is directly cut to small pieces, as electrode.By group
Dress button sodium ion half-cell, with VG@MoSe2@NC composite is half-cell positive pole, with
Whatman glass fibre is half-cell barrier film, with 1mol L-1NaClO4For solute, volume ratio is 1:1
Ethylene carbonate (EC) and dimethyl carbonate (DMC) be solvent, and add 5.0wt.% fluoro
Ethylene carbonate is electrolyte, and with sodium sheet for button half-cell negative pole, the assembling process of battery is all being filled
Full argon and water oxygen content complete less than in the glove box of 0.1ppm.
According to calculating of poor quality before and after reaction, nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid battle array can be calculated
MoSe in row sandwich structure sodium ion negative material2Content be about 0.26mg cm-2。
Nitrogen-doped carbon prepared by the present embodiment is coated with selenizing molybdenum/Graphene nucleocapsid array sandwich structure sodium
After ion negative material is assembled into sodium ion secondary battery, carry out various electrochemical property test.Sodium ion
Battery is at 200mA g-1There is under electric current density 783.5mAh g-1Discharge capacity first, through 400
After secondary circulation, its discharge capacity still has 535.8mAh g-1, coulombic efficiency maintains more than 99%, aobvious
Show capability retention and the cyclical stability of excellence.From the multiplying power of negative material prepared by the present embodiment
In performance map, this material shows the most excellent high rate performance, 0.2, and 0.5,1.0 and 2.0A g-1Electricity
Under current density, capacity respectively reaches 538,474,396 and 301mAh g-1.When electric current is from 2.0A g-1Return to
0.2A g-1Time, and after circulating 100 times, battery capacity returns to 537mAh g-1。
A kind of flexible nitrogen-doped carbon cladding selenizing molybdenum/sandwich knot of Graphene nucleocapsid array in embodiment 1～3
Structure sodium ion negative material is assembled into its maximum electric discharge under difference is in electric current density after sodium-ion battery
Capacity is as shown in table 1:
Table 1
Claims (10)
1. the system of the composite of nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure
Preparation Method, it is characterised in that comprise the following steps:
(1) selenium powder is dissolved in hydrazine hydrate, forms solution A；
(2) Sodium Molybdate Dihydrate is dissolved in water, forms solution B；
(3) solution A is mixed homogeneously with solution B, form reactant liquor, the vertical of carbon cloth will be grown in
Graphene collector material is placed in this reactant liquor, carries out hydro-thermal reaction, the most scrubbed, dry, washes
Wash, be dried, obtain VG-MoSe2Nucleocapsid array structure；
(4) take dopamine hydrochloride to be dissolved in water, form dopamine hydrochloride aqueous solution, then by step
(3) VG-MoSe of gained2Nucleocapsid array structure is immersed in dopamine hydrochloride aqueous solution, and water-bath gathers
Close, scrubbed dry, obtain the nucleocapsid array structure of dopamine polymerization；
(5) the nucleocapsid array structure being polymerized by step (4) gained dopamine, calcines under protective atmosphere
Carbonization, obtains the composite of nitrogen-doped carbon cladding selenizing molybdenum/Graphene nucleocapsid array sandwich structure.
Nitrogen-doped carbon the most according to claim 1 cladding selenizing molybdenum/sandwich knot of Graphene nucleocapsid array
The preparation method of the composite of structure, it is characterised in that in step (1), selenium in described solution A
Concentration be 0.2-0.6mmolmL-1。
Nitrogen-doped carbon the most according to claim 1 cladding selenizing molybdenum/sandwich knot of Graphene nucleocapsid array
The preparation method of the composite of structure, it is characterised in that in step (2), molybdenum in described solution B
The concentration of acid sodium is 0.02-0.1mmolmL-1。
Nitrogen-doped carbon the most according to claim 1 cladding selenizing molybdenum/sandwich knot of Graphene nucleocapsid array
The preparation method of the composite of structure, it is characterised in that in step (3), selenium in described solution A
It is 1.5～2.5:1 with the mol ratio of sodium molybdate in solution B.
Nitrogen-doped carbon the most according to claim 1 cladding selenizing molybdenum/sandwich knot of Graphene nucleocapsid array
The preparation method of the composite of structure, it is characterised in that in step (3), carry out water at 160-200 DEG C
Thermal response 12-24 hour.
Nitrogen-doped carbon the most according to claim 1 cladding selenizing molybdenum/sandwich knot of Graphene nucleocapsid array
The preparation method of the composite of structure, it is characterised in that in step (4), described dopamine hydrochloride
In aqueous solution, the concentration of dopamine is 3-7mg mL-1。
Nitrogen-doped carbon the most according to claim 1 cladding selenizing molybdenum/sandwich knot of Graphene nucleocapsid array
The preparation method of the composite of structure, it is characterised in that in step (4), gathers 70 DEG C of-90 DEG C of water-baths
Close 12-24 hour.
Nitrogen-doped carbon the most according to claim 1 cladding selenizing molybdenum/sandwich knot of Graphene nucleocapsid array
The preparation method of the composite of structure, it is characterised in that in step (5), described protective atmosphere is
Nitrogen or argon, calcining heat is 500-800 DEG C, and calcination time is 2-6h.
9. the nitrogen-doped carbon cladding selenizing prepared according to the preparation method described in any one of claim 1～8
The composite of molybdenum/Graphene nucleocapsid array sandwich structure.
Nitrogen-doped carbon the most according to claim 9 cladding selenizing molybdenum/sandwich knot of Graphene nucleocapsid array
The composite of structure is as the application of anode material of lithium-ion battery.
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